JP2003251364A - Treatment method for emulsion polymerization-based polymer-containing waste liquid - Google Patents
Treatment method for emulsion polymerization-based polymer-containing waste liquidInfo
- Publication number
- JP2003251364A JP2003251364A JP2002059245A JP2002059245A JP2003251364A JP 2003251364 A JP2003251364 A JP 2003251364A JP 2002059245 A JP2002059245 A JP 2002059245A JP 2002059245 A JP2002059245 A JP 2002059245A JP 2003251364 A JP2003251364 A JP 2003251364A
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- polymer
- added
- emulsion polymerization
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、乳化重合系ポリマ
ーの製造の際に排出される、乳化重合系ポリマー、乳化
剤等を含む廃液の処理方法に関する。TECHNICAL FIELD The present invention relates to a method for treating a waste liquid containing an emulsion-polymerized polymer, an emulsifier, etc., which is discharged during the production of an emulsion-polymerized polymer.
【０００２】[0002]
【従来の技術】従来より、乳化重合系ポリマーは、乳化
重合法によってポリマーを含むポリマーラテックスを製
造する重合工程、ポリマーラテックス中のポリマーを凝
集させてポリマースラリーとする凝固工程、洗浄と脱水
を繰り返しながらポリマースラリーから水、凝集剤等を
取り除き、最終的に水分率の低い脱水物を得る洗浄・脱
水工程、脱水物を乾燥させて粉粒体にする乾燥工程を経
て製造されている。2. Description of the Related Art Conventionally, emulsion polymerization type polymers have a polymerization step of producing a polymer latex containing a polymer by an emulsion polymerization method, a coagulation step of aggregating a polymer in the polymer latex into a polymer slurry, and repeating washing and dehydration. However, it is manufactured through a washing / dehydration step of finally removing water, a flocculant, etc. from the polymer slurry to obtain a dehydrated product having a low water content, and a drying process of drying the dehydrated product to form a granular material.
【０００３】乳化重合系ポリマーの製造の際には、洗浄
・脱水工程からは乳化重合系ポリマー、乳化剤等が含ま
れた廃液が排出され、また、乳化重合ポリマーの製造後
には、各工程の装置の洗浄によって、乳化重合系ポリマ
ーのエマルジョン、ラテックス等を含む洗浄廃液が排出
される。これら廃液中にはポリマーが多く含まれてお
り、このポリマーはＣＯＤ等の水質悪化要因となるた
め、そのまま一般排水として外部に放流することができ
ず、凝集沈澱処理などの廃液処理によってポリマーを回
収する必要がある。During the production of the emulsion-polymerized polymer, a waste liquid containing the emulsion-polymerized polymer, the emulsifier, etc. is discharged from the washing / dehydration step, and after the production of the emulsion-polymerized polymer, an apparatus for each step is used. By the washing, the washing waste liquid containing the emulsion polymerization type polymer emulsion, latex and the like is discharged. Since a large amount of polymer is contained in these waste liquids, and this polymer causes water quality deterioration such as COD, it cannot be directly discharged to the outside as general waste water, and the polymer is recovered by waste liquid treatment such as coagulation sedimentation treatment. There is a need to.
【０００４】従来より、乳化重合系ポリマーを含有する
廃液の凝集沈澱処理は、廃液中の乳化重合系ポリマーを
凝集させ、凝集体（フロック）を沈澱させ、上澄み液と
凝集体を分離したのち、上澄み液を一般排水として外部
に放流し、一方、凝集体を脱水して廃棄物として処分す
ることにより行われてきた。また、廃液中の乳化重合系
ポリマーを凝集させる方法としては、廃液に、アルミニ
ウム塩、マグネシウム塩、鉄塩等の無機凝集剤を添加す
る方法、または廃液に無機凝集剤を添加し、これにアニ
オン型、カチオン型等の高分子凝集剤から選ばれる１種
の高分子凝集剤をさらに添加する方法がとられてきた。[0004] Conventionally, in the coagulation-precipitation treatment of a waste liquid containing an emulsion polymerization type polymer, the emulsion polymerization type polymer in the waste liquid is aggregated to precipitate an aggregate (flock), and the supernatant liquid and the aggregate are separated, It has been carried out by discharging the supernatant liquid to the outside as general waste water, while dehydrating the aggregates and disposing as waste. Further, as a method for aggregating the emulsion-polymerized polymer in the waste liquid, a waste liquid, a method of adding an inorganic coagulant such as an aluminum salt, a magnesium salt, an iron salt, or an inorganic coagulant added to the waste liquid, and an anion A method of further adding one kind of polymer coagulant selected from polymer coagulants such as type and cationic type has been taken.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、無機凝
集剤のみ、もしくは無機凝集剤および１種の高分子凝集
剤を廃液に添加して乳化重合系ポリマーを沈澱が可能な
程度の粒径まで凝集させても、凝集体の凝集が不十分で
あり、分裂して小さな粒径の凝集体となりやすかった。
この小粒径の凝集体は、沈澱、分離しにくく、上澄み液
に残留するおそれがあり、上澄み液を再度、凝集し、廃
液処理する必要が生じる場合があった。However, the inorganic coagulant alone, or the inorganic coagulant and one kind of polymer coagulant are added to the waste liquid to coagulate the emulsion-polymerized polymer to a particle size that allows precipitation. However, the aggregation of the agglomerates was insufficient, and it was easy for the agglomerates to break up into agglomerates of small particle size.
This aggregate having a small particle size is difficult to precipitate and separate, and may remain in the supernatant liquid, and it may be necessary to aggregate the supernatant liquid again and treat the waste liquid.
【０００６】また、乳化重合系ポリマーを製造する工場
などにおいては、乳化重合系ポリマーの製造ラインは複
数あることが多く、これらラインから排出される廃液
は、含まれる乳化剤の種類がそれぞれ異なっていること
が多い。通常、廃液に添加される高分子凝集剤のイオン
性は、乳化重合系ポリマーを大粒径の凝集体とするため
に、乳化剤のイオン性に応じて適宜、選択されるが、廃
液にイオン性の異なる乳化剤が複数含まれている場合に
は、１種の高分子凝集剤では対応しきれず、大粒径の凝
集体を得にくく、小粒径の凝集体が上澄み液に残留する
おそれがあった。In addition, in a factory for producing an emulsion polymerization type polymer, there are often a plurality of emulsion polymerization type production lines, and the waste liquid discharged from these lines has different kinds of emulsifiers contained therein. Often. Usually, the ionicity of the polymer flocculant added to the waste liquid is appropriately selected according to the ionicity of the emulsifier in order to make the emulsion-polymerized polymer into an aggregate having a large particle size. When a plurality of different emulsifiers of different types are contained, one type of polymer flocculant cannot be used, it is difficult to obtain a large-sized aggregate, and a small-sized aggregate may remain in the supernatant. It was
【０００７】よって、本発明の目的は、乳化重合系ポリ
マーの凝集体の粒径を大きくし、凝集体の回収効率を向
上させ、放流される排水中の有機物含有量を減らすこと
ができる乳化重合系ポリマーを含有する廃液の処理方法
を提供することにある。Therefore, the object of the present invention is to increase the particle size of aggregates of emulsion polymerization type polymers, improve the collection efficiency of the aggregates, and reduce the content of organic substances in the discharged wastewater. It is an object of the present invention to provide a method for treating a waste liquid containing a base polymer.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明の乳化
重合系ポリマーを含有する廃液の処理方法は、乳化重合
系ポリマーを含有する廃液から乳化重合系ポリマーを凝
集、分離する処理方法において、乳化重合系ポリマーを
含有する廃液に硫酸アルミニウムを添加し、ついで、硫
酸アルミニウムが添加された廃液に第一の高分子凝集剤
を添加し、さらに、第一の高分子凝集剤が添加された廃
液に、第一の高分子凝集剤とは異なる電荷を有する第二
の高分子凝集剤を添加することを特徴とする。[Means for Solving the Problems] That is, a method for treating a waste liquid containing an emulsion polymerization type polymer of the present invention is a method for aggregating and separating an emulsion polymerization type polymer from a waste liquid containing an emulsion polymerization type polymer. Aluminum sulphate is added to the waste liquid containing the polymer, then the first polymer flocculant is added to the waste liquor containing aluminum sulphate, and the waste liquor containing the first polymer coagulant is further added. The second polymer flocculant having a charge different from that of the first polymer flocculant is added.
【０００９】また、本発明の乳化重合系ポリマーを含有
する廃液の処理方法においては、硫酸アルミニウムが添
加された廃液のｐＨを７〜１０の範囲に調整することが
望ましい。また、前記２種類の高分子凝集剤は、質量平
均分子量１０００万〜１５００万であるポリアクリルア
ミド系のアニオン型高分子凝集剤、および質量平均分子
量３５０万〜５００万であるポリアクリル酸エステル系
のカチオン型高分子凝集剤であることが望ましい。Further, in the method for treating a waste liquid containing the emulsion polymerization type polymer of the present invention, it is desirable to adjust the pH of the waste liquid containing aluminum sulfate to the range of 7 to 10. The two types of polymer flocculants include a polyacrylamide-based anionic polymer flocculant having a mass average molecular weight of 10,000,000 to 15,000,000 and a polyacrylate ester type having a mass average molecular weight of 3.5,000,000 to 5,000,000. It is preferably a cationic polymer flocculant.
【００１０】[0010]
【発明の実施の形態】以下、本発明について詳しく説明
する。本発明の乳化重合系ポリマーを含有する廃液の処
理方法は、硫酸アルミニウムが添加された廃液に、それ
ぞれ電荷の異なる第一の高分子凝集剤および第二の高分
子凝集剤（以下、これらを２種類の高分子凝集剤と記
す）を、それぞれ個別に添加することに特徴がある。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. A method for treating a waste liquid containing an emulsion-polymerized polymer of the present invention is a method in which a waste liquid containing aluminum sulfate is added to a first polymer coagulant and a second polymer coagulant (hereinafter Each type of polymer coagulant) is added individually.
【００１１】本発明においては、乳化重合系ポリマーの
凝集能力に優れることから、無機凝集剤として硫酸アル
ミニウムが使用される。硫酸アルミニウムの添加量は、
特に限定はされないが、乳化重合系ポリマーが凝集し、
凝集体となる程度が好ましく、通常、廃液中の乳化重合
系ポリマー（固形分）１００質量部に対して０．３〜１
０質量部の範囲である。In the present invention, aluminum sulfate is used as an inorganic flocculant because it has excellent flocculation ability of the emulsion polymer. The amount of aluminum sulfate added is
Although not particularly limited, the emulsion-polymerized polymer aggregates,
Aggregate is preferable, and usually 0.3 to 1 with respect to 100 parts by mass of the emulsion-polymerized polymer (solid content) in the waste liquid.
The range is 0 parts by mass.
【００１２】硫酸アルミニウムが添加された廃液は、乳
化重合系ポリマーの凝集を促進し、大粒径の凝集体を生
成しやすくするために、そのｐＨが７〜１０の範囲に調
整されることが好ましい。廃液のｐＨが７未満では、乳
化重合系ポリマーの凝集が弱く、大粒径の凝集体を生成
し難くなるおそれがあり、一方、廃液のｐＨが１０を超
えると、同じく大粒径の凝集体を生成し難くなるおそれ
がある。 硫酸アルミニウムが添加された廃液のｐＨ
は、より好ましくは７．５〜９．５の範囲であり、さら
に好ましくは８．０〜９．０の範囲である。硫酸アルミ
ニウムが添加された廃液は酸性となっているので、この
廃液のｐＨを７〜１０の範囲に調整するためには、水酸
化ナトリウム水溶液等のアルカリ性水溶液が使用され
る。The pH of the waste liquid to which aluminum sulfate is added may be adjusted within the range of 7 to 10 in order to accelerate the aggregation of the emulsion-polymerized polymer and facilitate the production of aggregates of large particle size. preferable. If the pH of the waste liquid is less than 7, aggregation of the emulsion-polymerized polymer may be weak and it may be difficult to form aggregates having a large particle size. On the other hand, if the pH of the waste liquid exceeds 10, aggregates having a large particle size may also be generated. May be difficult to generate. PH of waste liquid containing aluminum sulfate
Is more preferably in the range of 7.5 to 9.5, and further preferably in the range of 8.0 to 9.0. Since the waste liquid to which aluminum sulfate is added is acidic, an alkaline aqueous solution such as a sodium hydroxide aqueous solution is used to adjust the pH of this waste liquid to the range of 7 to 10.
【００１３】２種類の高分子凝集剤としては、それぞれ
電荷が異なる高分子凝集剤、すなわちアニオン型高分子
凝集剤およびカチオン型高分子凝集剤が使用される。ア
ニオン型高分子凝集剤としては、例えば、アクリルアミ
ドと、（メタ）アクリル酸、２−アクリルアミド−２−
メチルプロパンスルホン酸、ビニルスルホン酸またはこ
れらの塩との共重合体、ポリアクリルアミドの部分加水
分解物等のアクリルアミド系高分子凝集剤；アクリル酸
と水酸化ナトリウムからつくられるポリアクリル酸ソー
ダ系高分子凝集剤などが挙げられる。As the two types of polymer coagulants, polymer coagulants having different charges, that is, anionic polymer coagulant and cationic polymer coagulant are used. Examples of the anionic polymer flocculant include acrylamide, (meth) acrylic acid, 2-acrylamide-2-
Acrylamide-based polymer flocculants such as methyl propane sulfonic acid, copolymers with vinyl sulfonic acid or salts thereof, and partial hydrolysis products of polyacrylamide; polyacrylic acid sodium-based polymers made from acrylic acid and sodium hydroxide Examples thereof include a flocculant.
【００１４】中でも、ポリアクリルアミド系のアニオン
型高分子凝集剤が、乳化重合系ポリマーの凝集能力に優
れることから好適に用いられる。また、ポリアクリルア
ミド系のアニオン型高分子凝集剤の質量平均分子量は、
１０００万〜１５００万の範囲であることが好ましい。
質量平均分子量が１０００万未満では、凝集力が不十分
となり、小さな粒径の凝集体となりやすい。一方、質量
平均分子量が１５００万を超えると、同様に凝集力が不
十分となり、小さな粒径の凝集体となりやすい。アニオ
ン型高分子凝集剤の添加量は、特に限定はされないが、
通常、廃液に対して０．２〜１００００ｐｐｍの範囲で
ある。Among them, polyacrylamide type anionic polymer flocculants are preferably used because they are excellent in flocculation ability of emulsion polymerization type polymers. The mass average molecular weight of the polyacrylamide-based anionic polymer flocculant is
It is preferably in the range of 10 to 15 million.
If the mass average molecular weight is less than 10 million, the cohesive force becomes insufficient and the aggregates having a small particle size are likely to be formed. On the other hand, when the mass average molecular weight exceeds 15,000,000, the cohesive force is similarly insufficient and the aggregates having a small particle size are likely to be formed. The addition amount of the anionic polymer flocculant is not particularly limited,
Usually, it is in the range of 0.2 to 10,000 ppm with respect to the waste liquid.
【００１５】カチオン型高分子凝集剤としては、解離し
てカチオン性となるアクリル酸エステル化合物を単量体
単位として含有するポリアクリル酸エステル系高分子凝
集剤、ポリアミン系高分子凝集剤、ジシアンジアミド系
高分子凝集剤などが挙げられる。As the cationic polymer flocculant, a polyacrylic ester polymer flocculant, a polyamine polymer flocculant, and a dicyandiamide polymer containing an acrylic ester compound as a monomer unit which dissociates to become cationic. Polymer flocculants and the like can be mentioned.
【００１６】中でも、ポリアクリル酸エステル系のカチ
オン型高分子凝集剤が、乳化重合系ポリマーの凝集能力
に優れることから好適に用いられる。また、ポリアクリ
ル酸エステル系のカチオン型高分子凝集剤の質量平均分
子量は、３５０万〜５００万の範囲であることが好まし
い。質量平均分子量が３５０万未満では、凝集力が不十
分となり、小さな粒径の凝集体となりやすい。一方、質
量平均分子量が５００万を超えると、同様に凝集力が不
十分となり、小さな粒径の凝集体となりやすい。 カチ
オン型高分子凝集剤の添加量は、特に限定はされない
が、通常、廃液に対して０．２〜１００００ｐｐｍの範
囲である。Among them, a polyacrylic acid ester type cationic polymer flocculant is preferably used because it is excellent in the flocculation ability of the emulsion polymerization type polymer. The mass average molecular weight of the polyacrylic acid ester-based cationic polymer flocculant is preferably in the range of 3.5 million to 5 million. When the mass average molecular weight is less than 3.5 million, the cohesive force becomes insufficient, and the aggregate having a small particle size is likely to be formed. On the other hand, when the mass average molecular weight exceeds 5,000,000, the cohesive force is similarly insufficient and the aggregates having a small particle size are likely to be formed. The addition amount of the cationic polymer flocculant is not particularly limited, but is usually in the range of 0.2 to 10000 ppm with respect to the waste liquid.
【００１７】アニオン型高分子凝集剤およびカチオン型
高分子凝集剤は、個別に廃液に添加され、同時に添加さ
れることはない。添加の順序、すなわちアニオン型とカ
チオン型のどちらを第一の高分子凝集剤とし、どちらを
第二の高分子凝集剤とするかは、特に限定はされない
が、廃液に含まれる乳化剤のイオン性に応じて決定され
ることが好ましい。すなわち、廃液に含まれている乳化
剤がアニオン性である、もしくは廃液に含まれている乳
化剤が複数種類であって、アニオン性の乳化剤が多く含
まれている場合は、まず、カチオン型高分子凝集剤を廃
液に添加し、続いてアニオン型高分子凝集剤を添加する
ことが、凝集効率の点から好ましい。また、廃液に含ま
れている乳化剤がカチオン性である、もしくは廃液に含
まれている乳化剤が複数種類であって、カチオン性の乳
化剤が多く含まれている場合は、まず、アニオン型高分
子凝集剤を廃液に添加し、続いてカチオン型高分子凝集
剤を添加することが、凝集効率の点から好ましい。The anionic polymer flocculant and the cationic polymer flocculant are individually added to the waste liquid and are not simultaneously added. The order of addition, that is, which of the anionic type and the cationic type is the first polymer flocculant and which is the second polymer flocculant is not particularly limited, but the ionicity of the emulsifier contained in the waste liquid is not limited. Is preferably determined according to That is, when the emulsifier contained in the waste liquid is anionic, or when the waste liquid contains a plurality of types of emulsifiers and contains a large amount of anionic emulsifier, first, the cationic polymer coagulation is used. From the viewpoint of aggregation efficiency, it is preferable to add the agent to the waste liquid and then add the anionic polymer flocculant. If the emulsifier contained in the waste liquid is cationic, or if there are multiple kinds of emulsifiers contained in the waste liquid and a large amount of the cationic emulsifier is contained, first, the anionic polymer aggregates are aggregated. From the viewpoint of aggregation efficiency, it is preferable to add the agent to the waste liquid and then add the cationic polymer flocculant.
【００１８】廃液に含まれる乳化剤としては、アニオン
性、カチオン性、両性、非イオン性の界面活性剤が挙げ
られる。アニオン性の界面活性剤としては、例えば、脂
肪酸塩タイプ、硫酸エステル塩タイプ、スルホン酸塩タ
イプ、リン酸エステル塩タイプなどが挙げられる。カチ
オン性の界面活性剤としては、アルキルアミン塩タイ
プ、第４級アンモニウム塩タイプなどが挙げられる。両
性の界面活性剤としては、例えば、アルキルベタインタ
イプ、アミンオキサイドタイプなどが挙げられる。非イ
オン性の界面活性剤としては、例えば、ポリオキシエチ
レンタイプ、ソルビタンエステルタイプ、リン酸エステ
ル塩タイプなどが挙げられる。Examples of emulsifiers contained in the waste liquid include anionic, cationic, amphoteric and nonionic surfactants. Examples of the anionic surfactant include fatty acid salt type, sulfate ester salt type, sulfonate salt type, and phosphate ester salt type. Examples of the cationic surfactant include alkylamine salt type and quaternary ammonium salt type. Examples of the amphoteric surfactant include alkyl betaine type and amine oxide type. Examples of the nonionic surfactant include polyoxyethylene type, sorbitan ester type, and phosphoric acid ester salt type.
【００１９】硫酸アルミニウム、および電荷の異なる２
種類の高分子凝集剤を、それぞれ個別に添加することに
よって、乳化重合系ポリマーを主成分とする凝集体が生
成した廃液は、公知の分離方法によって上澄み液と凝集
体とに分離される。分離方法としては、例えば、重力沈
降による重力沈降法、遠心濃縮法、膜分離法等が挙げら
れる。Aluminum sulfate and 2 having different charges
The waste liquid in which the aggregates containing the emulsion polymerization type polymer as the main component are produced by adding the respective types of high-molecular aggregating agents individually is separated into a supernatant and an aggregate by a known separation method. Examples of the separation method include a gravity sedimentation method by gravity sedimentation, a centrifugal concentration method, a membrane separation method, and the like.
【００２０】このようにして分離された凝集体は、脱水
されて、最終的に廃棄物として処分される。凝集体の脱
水方法としては、例えば、ベルトプレス脱水法、遠心脱
水法、スクリュープレス脱水法、フィルタープレス脱水
法等の公知の方法を適用できる。The agglomerates thus separated are dehydrated and finally disposed of as waste. As a method for dehydrating the aggregate, known methods such as a belt press dehydration method, a centrifugal dehydration method, a screw press dehydration method, and a filter press dehydration method can be applied.
【００２１】以上説明したような乳化重合系ポリマーを
含有する廃液の処理方法においては、まず、乳化重合系
ポリマーを含有する廃液に硫酸アルミニウムを添加する
ことにより、乳化重合系ポリマーが凝集して比較的小粒
径の凝集体が生成する。ついで、硫酸アルミニウムが添
加された廃液に第一の高分子凝集剤を添加することによ
り、小粒径の凝集体がさらに集合して比較的大粒径の凝
集体が生成する。さらに、第一の高分子凝集剤が添加さ
れた廃液に、第一の高分子凝集剤とは異なる電荷を有す
る第二の高分子凝集剤を添加することにより、第二の高
分子凝集剤が、凝集体中に取り込まれた第一の高分子凝
集剤とイオン的に結合し、凝集体間の架橋剤としての役
割を果たし、巨大な凝集体の集合体が形成される。In the method for treating the waste liquid containing the emulsion-polymerized polymer as described above, first, aluminum sulfate is added to the waste liquid containing the emulsion-polymerized polymer so that the emulsion-polymerized polymer is aggregated and compared. Agglomerates of relatively small particle size are formed. Then, by adding the first polymer coagulant to the waste liquid containing aluminum sulfate, the aggregates having a small particle size are further aggregated to form the aggregates having a relatively large particle size. Furthermore, by adding a second polymer flocculant having a charge different from that of the first polymer flocculant to the waste liquid to which the first polymer flocculant is added, , Ionically binds to the first polymer coagulant incorporated in the aggregate, and acts as a cross-linking agent between the aggregates, forming a huge aggregate of aggregates.
【００２２】この凝集体の集合体は、沈降速度が速いの
で、廃液処理の効率が格段に良くなる。また、この凝集
体の集合体は、電荷の異なる２種類の高分子凝集剤のイ
オン結合によって強固に集合しているので、分裂しにく
い。したがって、沈澱、分離しにくい小粒径の凝集体の
発生を抑えることができ、凝集体の回収効率を向上さ
せ、放流される排水中の有機物含有量を減らすことがで
きる。Since the aggregate of aggregates has a high sedimentation speed, the efficiency of waste liquid treatment is remarkably improved. In addition, this aggregate of aggregates is firmly aggregated by the ionic bond of two types of polymer aggregating agents having different charges, and thus is difficult to be divided. Therefore, it is possible to suppress the generation of aggregates having a small particle size that are difficult to precipitate and separate, improve the efficiency of collecting the aggregates, and reduce the content of organic substances in the discharged wastewater.
【００２３】また、廃液に電荷の異なる２種類の高分子
凝集剤を添加しているので、廃液中にイオン性の異なる
複数種類の乳化剤が含まれていたとしても、高分子凝集
剤による凝集能力を低下させることはなく、これによ
り、凝集体の回収効率を向上させ、放流される排水中の
有機物含有量を減らすことができる。Further, since two kinds of polymer coagulants having different charges are added to the waste liquid, even if the waste liquid contains plural kinds of emulsifiers having different ionic properties, the coagulation ability of the polymer coagulant is high. By so doing, it is possible to improve the collection efficiency of aggregates and reduce the content of organic substances in the discharged wastewater.
【００２４】[0024]
【実施例】以下に実施例を示して、本発明をさらに説明
するが、本発明はこれらの実施例に限定されるものでは
ない。また、本実施例では、「部」および「％」は、特
に断りがない限り、「質量部」および「質量％」を意味
する。また、本実施例においては、凝集体（フロック）
の大きさは、下記の方法で測定される凝集体の沈降速度
で表した。The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Further, in the present examples, “parts” and “%” mean “parts by mass” and “mass%” unless otherwise specified. In addition, in this example, aggregates (flocks)
The size of was indicated by the sedimentation rate of the aggregate measured by the following method.
【００２５】（沈降速度）フロックが形成された排水を
５００ｍｌのメスシリンダーに採取した後静置し、フロ
ックと水が完全に分離するまでの時間を沈降速度とし
た。(Settling Speed) The waste water on which flocs were formed was sampled in a 500 ml graduated cylinder and allowed to stand still, and the time until the flocs and water were completely separated was defined as the sedimentation speed.
【００２６】また、本実施例においては、乳化重合系ポ
リマーを含有する廃液として、以下の廃液を使用した。
（廃液Ａ）乳化重合系ポリマーとしてメタクリル酸メチ
ル／ブタジエン／スチレン共重合体を製造した際に排出
された廃液（排水）であり、浮遊懸濁物質（以下ＳＳと
略す）を１．２％、乳化剤として脂肪酸塩タイプのアニ
オン性界面活性剤（花王（株）製、ＫＳソープＭＲ）を
１５０ｐｐｍ含有するものである。Further, in this example, the following waste liquids were used as the waste liquid containing the emulsion polymer. (Waste liquid A) Waste liquid (drainage) discharged when a methyl methacrylate / butadiene / styrene copolymer was produced as an emulsion-polymerization polymer, 1.2% of a suspended suspended substance (hereinafter abbreviated as SS), The emulsifier contains 150 ppm of a fatty acid salt type anionic surfactant (KS Soap MR, manufactured by Kao Corporation).
【００２７】（廃液Ｂ）乳化重合系ポリマーとしてメタ
クリル酸メチル／ブタジエン／スチレン共重合体および
シリコーンゴムを製造した際に排出された廃液（排水）
であり、ＳＳを１．８％、乳化剤として脂肪酸塩タイプ
のアニオン性界面活性剤（花王（株）製、ＫＳソープＭ
Ｒ）を１３０ｐｐｍ、スルホン酸塩タイプのアニオン性
界面活性剤（花王（株）製、ＫＳソープＭＲ）を３５０
ｐｐｍ含有するものである。(Waste liquid B) A waste liquid (drainage) discharged when a methyl methacrylate / butadiene / styrene copolymer and a silicone rubber are produced as an emulsion polymer.
And 1.8% SS, and anionic surfactant of fatty acid salt type as an emulsifier (manufactured by Kao Corporation, KS Soap M)
R) is 130 ppm, and a sulfonate type anionic surfactant (KS Soap MR, manufactured by Kao Corporation) is 350 ppm.
ppm content.
【００２８】（廃液Ｃ）乳化重合系ポリマーとしてメタ
クリル酸メチル／ブタジエン／スチレン共重合体、シリ
コーンゴムおよびアクリルゴムを製造した際に排出され
た廃液（排水）であり、ＳＳを２．８％、乳化剤として
脂肪酸塩タイプのアニオン性界面活性剤（花王（株）
製、ＫＳソープＭＲ）を１１０ｐｐｍ、スルホン酸塩タ
イプのアニオン性界面活性剤（花王（株）製、ＫＳソー
プＭＲ）を３８０ｐｐｍ、リン酸エステル塩タイプの非
イオン性アニオン界面活性剤（東邦化学製、フォスファ
ノールＬＯ−５２９）を２００ｐｐｍ含有するものであ
る。(Waste liquid C) This is a waste liquid (wastewater) discharged when a methyl methacrylate / butadiene / styrene copolymer, a silicone rubber and an acrylic rubber were produced as an emulsion polymer, and SS was 2.8%. Fatty acid salt type anionic surfactant as emulsifier (Kao Corporation)
Manufactured by KS Soap MR) of 110 ppm, sulfonate type anionic surfactant (KS Soap MR manufactured by Kao Corporation) of 380 ppm, phosphate ester salt type nonionic anionic surfactant (manufactured by Toho Chemical Co., Ltd.). , Phosphanol LO-529) in an amount of 200 ppm.
【００２９】［実施例１］まず、廃液Ａ１００部に硫酸
アルミニウム２部を添加し、これに２％水酸化ナトリウ
ム水溶液を加えてｐＨ７．５に調整し、５分間攪拌し
た。ついで、硫酸アルミニウムが添加された廃液に、ポ
リアクリル酸エステル系のカチオン型高分子凝集剤（ダ
イヤフロック（株）製、ＫＰ−２０４Ｂ、質量平均分子
量４００万）５００ｐｐｍを添加し、１分間攪拌した。
さらに、この廃液に、ポリアクリルアミド系のアニオン
型高分子凝集剤（ダイヤフロック（株）製、ＡＰ−１２
０、質量平均分子量１１００万）５００ｐｐｍを添加、
１分間攪拌した。廃液中の凝集体の沈降速度を測定し
た。結果を表１に示す。Example 1 First, 2 parts of aluminum sulfate was added to 100 parts of waste liquid A, and a 2% aqueous sodium hydroxide solution was added to adjust the pH to 7.5, followed by stirring for 5 minutes. Then, 500 ppm of a polyacrylic acid ester-based cationic polymer flocculant (manufactured by Diafloc Co., Ltd., KP-204B, mass average molecular weight 4,000,000) was added to the waste liquid containing aluminum sulfate, and the mixture was stirred for 1 minute. .
Furthermore, this waste liquid was added with a polyacrylamide-based anionic polymer flocculant (AP-12, manufactured by Diafloc Co., Ltd.).
0, mass average molecular weight 11 million) 500 ppm added,
Stir for 1 minute. The sedimentation rate of aggregates in the waste liquid was measured. The results are shown in Table 1.
【００３０】［実施例２］廃液Ａを廃液Ｂに変更した以
外は、実施例１と同様にして廃液処理を行い、廃液中の
凝集体の沈降速度を測定した。結果を表１に示す。[Example 2] Waste liquid treatment was performed in the same manner as in Example 1 except that waste liquid A was changed to waste liquid B, and the sedimentation rate of aggregates in the waste liquid was measured. The results are shown in Table 1.
【００３１】［実施例３］廃液Ａを廃液Ｃに変更した以
外は、実施例１と同様にして廃液処理を行い、廃液中の
凝集体の沈降速度を測定した。結果を表１に示す。[Example 3] Waste liquid treatment was performed in the same manner as in Example 1 except that the waste liquid A was changed to the waste liquid C, and the sedimentation rate of aggregates in the waste liquid was measured. The results are shown in Table 1.
【００３２】［比較例１］カチオン型およびアニオン型
高分子凝集剤を添加せず、硫酸アルミニウムの添加量を
２部に変更した以外は、実施例３と同様にして廃液処理
を行い、廃液中の凝集体の沈降速度を測定した。結果を
表１に示す。[Comparative Example 1] Waste liquid was treated in the same manner as in Example 3 except that the cationic and anionic polymer flocculants were not added and the amount of aluminum sulfate added was changed to 2 parts. The sedimentation rate of the aggregates was measured. The results are shown in Table 1.
【００３３】［比較例２］カチオン型高分子凝集剤を添
加せず、硫酸アルミニウムの添加量を２部に、アニオン
型高分子凝集剤の添加量を１０００ｐｐｍに変更した以
外は、実施例３と同様にして廃液処理を行い、廃液中の
凝集体の沈降速度を測定した。結果を表１に示す。[Comparative Example 2] The same as Example 3 except that the cationic polymer flocculant was not added, the amount of aluminum sulfate added was changed to 2 parts, and the amount of anionic polymer flocculant added was changed to 1000 ppm. Waste liquid treatment was performed in the same manner, and the sedimentation rate of aggregates in the waste liquid was measured. The results are shown in Table 1.
【００３４】［比較例３］アニオン型高分子凝集剤を添
加せず、硫酸アルミニウムの添加量を２部に、カチオン
型高分子凝集剤の添加量を１０００ｐｐｍに変更した以
外は、実施例３と同様にして廃液処理を行い、廃液中の
凝集体の沈降速度を測定した。結果を表１に示す。[Comparative Example 3] Comparative Example 3 was repeated except that the anionic polymer flocculant was not added, the amount of aluminum sulfate added was changed to 2 parts, and the amount of the cationic polymer flocculant was changed to 1000 ppm. Waste liquid treatment was performed in the same manner, and the sedimentation rate of aggregates in the waste liquid was measured. The results are shown in Table 1.
【００３５】［比較例４］硫酸アルミニウムを添加せ
ず、カチオン型高分子凝集剤の添加量を１０００ｐｐｍ
に、アニオン型高分子凝集剤の添加量を１０００ｐｐｍ
に変更した以外は、実施例３と同様にして廃液処理を行
い、廃液中の凝集体の沈降速度を測定した。結果を表１
に示す。[Comparative Example 4] The addition amount of the cationic polymer flocculant was 1000 ppm without adding aluminum sulfate.
The addition amount of the anionic polymer flocculant is 1000 ppm
Waste liquid treatment was carried out in the same manner as in Example 3 except that the above was changed to, and the sedimentation rate of aggregates in the waste liquid was measured. The results are shown in Table 1.
Shown in.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【発明の効果】以上説明したように、本発明の乳化重合
系ポリマーを含有する廃液の処理方法は、乳化重合系ポ
リマーを含有する廃液に硫酸アルミニウムを添加し、つ
いで、硫酸アルミニウムが添加された廃液に第一の高分
子凝集剤を添加し、さらに、第一の高分子凝集剤が添加
された廃液に、第一の高分子凝集剤とは異なる電荷を有
する第二の高分子凝集剤を添加する方法であるので、乳
化重合系ポリマーの凝集体の粒径を大きくし、凝集体の
回収効率を向上させ、放流される排水中の有機物含有量
を減らすことができる。As described above, in the method for treating a waste liquid containing the emulsion polymerization type polymer of the present invention, aluminum sulfate is added to the waste liquid containing the emulsion polymerization type polymer, and then aluminum sulfate is added. The first polymer flocculant is added to the waste liquid, and the second polymer flocculant having a charge different from that of the first polymer flocculant is further added to the waste liquid containing the first polymer flocculant. Since it is a method of adding, the particle size of the aggregate of the emulsion polymerization type polymer can be increased, the collection efficiency of the aggregate can be improved, and the content of organic substances in the discharged wastewater can be reduced.
【００３８】また、硫酸アルミニウムが添加された廃液
のｐＨを７〜１０の範囲に調整すれば、乳化重合系ポリ
マーの凝集が促進され、大粒径の凝集体が生成しやすく
なり、廃液処理の効率がさらに向上する。また、前記２
種類の高分子凝集剤が、質量平均分子量１０００万〜１
５００万であるポリアクリルアミド系のアニオン型高分
子凝集剤、および質量平均分子量３５０万〜５００万で
あるポリアクリル酸エステル系のカチオン型高分子凝集
剤であれば、乳化系ポリマーの製造で排出されるポリマ
ーを主成分とする浮遊懸濁物質を効率よく凝集させ、大
粒径の凝集体を形成させることにより廃水処理の効率が
大幅に向上する。When the pH of the waste liquid containing aluminum sulfate is adjusted to the range of 7 to 10, aggregation of the emulsion-polymerized polymer is promoted, and large-sized aggregates are easily formed, which makes it easier to treat the waste liquid. Efficiency is further improved. Also, the above 2
The types of polymer flocculants have a mass average molecular weight of 10,000,000 to 1
5 million polyacrylamide type anionic polymer flocculants and polyacrylic acid ester type cationic polymer flocculants having a mass average molecular weight of 3.5 million to 5 million are discharged in the production of emulsion polymers. The efficiency of wastewater treatment is greatly improved by efficiently aggregating the suspended suspended matter containing a polymer as a main component to form an agglomerate having a large particle size.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D015 BA12 BA19 BB09 BB14 CA08 DA05 DB07 DB08 DB14 DB23 DC07 EA14 EA15 EA32 EA37 EA39 FA03 FA19 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4D015 BA12 BA19 BB09 BB14 CA08 DA05 DB07 DB08 DB14 DB23 DC07 EA14 EA15 EA32 EA37 EA39 FA03 FA19
Claims (3)
乳化重合系ポリマーを凝集、分離する処理方法におい
て、 乳化重合系ポリマーを含有する廃液に硫酸アルミニウム
を添加し、ついで、硫酸アルミニウムが添加された廃液
に第一の高分子凝集剤を添加し、さらに、第一の高分子
凝集剤が添加された廃液に、第一の高分子凝集剤とは異
なる電荷を有する第二の高分子凝集剤を添加することを
特徴とする乳化重合系ポリマーを含有する廃液の処理方
法。1. In a treatment method for aggregating and separating an emulsion polymerization type polymer from a waste solution containing an emulsion polymerization type polymer, aluminum sulfate is added to the waste solution containing the emulsion polymerization type polymer, and then aluminum sulfate is added. The first polymer flocculant is added to the waste liquid, and the second polymer flocculant having a charge different from that of the first polymer flocculant is further added to the waste liquid containing the first polymer flocculant. A method for treating a waste liquid containing an emulsion-polymerized polymer, which is characterized in that it is added.
Ｈを７〜１０の範囲に調整することを特徴とする請求項
１記載の乳化重合系ポリマーを含有する廃液の処理方
法。2. The p of the waste liquid containing aluminum sulfate added.
The method for treating a waste liquid containing an emulsion-polymerized polymer according to claim 1, wherein H is adjusted to a range of 7 to 10.
分子量１０００万〜１５００万であるポリアクリルアミ
ド系のアニオン型高分子凝集剤、および質量平均分子量
３５０万〜５００万であるポリアクリル酸エステル系の
カチオン型高分子凝集剤であることを特徴とする請求項
１または請求項２記載の乳化重合系ポリマーを含有する
廃液の処理方法。3. The polyacrylamide anionic polymer flocculant having a mass average molecular weight of 10,000,000 to 15,000,000, and polyacrylic acid having a weight average molecular weight of 3.5,000,000 to 5,000,000. The method for treating a waste liquid containing an emulsion-polymerized polymer according to claim 1 or 2, which is an ester-based cationic polymer flocculant.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002059245A JP3740423B2 (en) | 2002-03-05 | 2002-03-05 | Method for treating waste liquid containing emulsion polymerization polymer |
| CNB031051642A CN1276944C (en) | 2002-03-05 | 2003-03-03 | Treatment method of waste liquid containing emulsion polymerized polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002059245A JP3740423B2 (en) | 2002-03-05 | 2002-03-05 | Method for treating waste liquid containing emulsion polymerization polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003251364A true JP2003251364A (en) | 2003-09-09 |
| JP3740423B2 JP3740423B2 (en) | 2006-02-01 |
Family
ID=27800150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002059245A Expired - Fee Related JP3740423B2 (en) | 2002-03-05 | 2002-03-05 | Method for treating waste liquid containing emulsion polymerization polymer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3740423B2 (en) |
| CN (1) | CN1276944C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006007208A (en) * | 2004-05-26 | 2006-01-12 | Sanyo Chem Ind Ltd | Method for treating waste water containing resin particle |
| JP2010247118A (en) * | 2009-04-20 | 2010-11-04 | Momentive Performance Materials Inc | METHOD OF REDUCING CODCr IN HIGH CONCENTRATION SILICONE WASTE LIQUID |
| WO2017169050A1 (en) * | 2016-03-30 | 2017-10-05 | 住友重機械エンバイロメント株式会社 | Wastewater treatment system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110015735B (en) * | 2019-04-10 | 2022-03-22 | 深圳市松柏实业发展有限公司 | Composite flocculant, flocculation method thereof, recycling method and recycling system |
-
2002
- 2002-03-05 JP JP2002059245A patent/JP3740423B2/en not_active Expired - Fee Related
-
2003
- 2003-03-03 CN CNB031051642A patent/CN1276944C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006007208A (en) * | 2004-05-26 | 2006-01-12 | Sanyo Chem Ind Ltd | Method for treating waste water containing resin particle |
| JP2010247118A (en) * | 2009-04-20 | 2010-11-04 | Momentive Performance Materials Inc | METHOD OF REDUCING CODCr IN HIGH CONCENTRATION SILICONE WASTE LIQUID |
| WO2017169050A1 (en) * | 2016-03-30 | 2017-10-05 | 住友重機械エンバイロメント株式会社 | Wastewater treatment system |
| JP2017176999A (en) * | 2016-03-30 | 2017-10-05 | 住友重機械エンバイロメント株式会社 | Wastewater treatment system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3740423B2 (en) | 2006-02-01 |
| CN1442443A (en) | 2003-09-17 |
| CN1276944C (en) | 2006-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6617402B2 (en) | Polymer flocculants with improved dewatering characteristics | |
| JPH04298300A (en) | Sludge dehydrating agent and method for dehydrating sludge by using this agent | |
| AU703304B2 (en) | Method for using novel high solids polymer compositions as flocculation aids | |
| JP2013248584A (en) | Method for treating drainage | |
| JP3550955B2 (en) | Sludge treatment equipment | |
| JP6134940B2 (en) | Coagulation treatment method for oil-containing cleaning wastewater | |
| JPH10249398A (en) | Method for dehydrating sludge | |
| JP2003251364A (en) | Treatment method for emulsion polymerization-based polymer-containing waste liquid | |
| JP2008080185A (en) | Sludge dewatering method | |
| JPH10249400A (en) | Method for dehydrating sludge | |
| JP2002540941A (en) | More active dispersing polymer to aid purification, dewatering and retention and drainage | |
| JP4029021B2 (en) | Sludge dewatering agent and sludge dewatering method | |
| JP2017209651A (en) | Paper pulp sludge treatment method | |
| JP3906636B2 (en) | Amphoteric polymer flocculant and sludge dewatering method | |
| JP2014158993A (en) | Flocculation method of oil inclusion cleaning waste water | |
| JPH05185074A (en) | Treating agent for multivalent metal-containing water and treatment of the same | |
| CN106496404B (en) | Polyacrylate polymer dispersion liquid | |
| JPH10249399A (en) | Method for dehydrating sludge | |
| JP2001129311A (en) | Polymer flocculant and production of the same and dewatering method of organic sludge | |
| JP6387337B2 (en) | Method for removing suspended matter in water using a flocculating / flocculating material for cross-linked suspension material, and flocculating / flocculating agent for suspended material for suspension material removal treatment | |
| JPH0976000A (en) | Sludge dehydrating method | |
| JP4177513B2 (en) | Emulsion and flocculant compositions | |
| JPH10192899A (en) | Method for treating dredged sludge | |
| JP3141766B2 (en) | Sludge dewatering method | |
| JP2002205074A (en) | Treatment method for inorganic particle suspension |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050701 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050809 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050930 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20051025 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20051107 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 3740423 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091111 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091111 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101111 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111111 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111111 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111111 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121111 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121111 Year of fee payment: 7 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121111 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121111 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121111 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131111 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |